Colour photography



COLOUR PHOTOGRAPHY 7,

"Dennis Peter Ayres and: Douglas James'Fi'y, llfo'rd, England, assignors to Iltord Limited, Ilford, England, a British company 7 Ns nr'awing Application January 16,1956

' Serial No.- 59;101

Claims priority,appliisationGreatBritaint; I January29;1955

6 Claims. (Cl. 260-471) This invention relates to colourphotography and in particu'larto rocesses of colour photography in which developmentofa'silver image in a silver halidep'liotog'raphic emul'sionilayer is effected by meansof a" developing substance, the oxidatio'nproducts of which con thinewith a so-called colour-coupler; present in the system to form a dyestuti image in situ with the silver image. Such proces'ses' ar'e commonly referredto asprocesses of chromo genic: development. The developing agent employed is inorrnally an aromaticzprimary/ amino compound such{ as N,N.-dieth yl: p phenylamine diamine. 'I he'- colourcouplers. employed are commonly; substituted phenols or naphthols, or compounds containing a reactive methylene group, the dyestuffsiormed being indophenol or ammethine types of dye.

Tests. carried out on: a'nurnber o'f colour couplers" yielding. yellow dyestuffs. have revealed thatthe dyestuffs'have much less absorption in the violet and-ultraviolet regions of the spectrum than. they. have in theblue region-f the spectrum= This relative transparency is a. disadvantage in certain respects. Thus, when a colour transparency containing such a yellow image layer is copied on to a print. material, the yellow dye image permits the transmissi'onof a high proportion of violet and ulta-violet radi- 'ation from. the-exposing light; and thisradiation affects,

and to some extentfalsifies, the recordingon the p'r iiit'ed material. This disadvantage is accentuated if-the silfver halide. emulsion ofi the pri'nt material is on'e' which is 'itselfwhere R and R are'alkyl' groupscontaining up to 4 car- ,bon atomsand R is an aromatic grouping or a substitutedaroma'tic grouping. Thus, tlie'group R may be a .ben'zene or naphthalene group and may carry one or more subs'tituents selected from any of the following: alkyl,

' e.= g; methyl, ethyl,,propyland higher alkyl such'asalkyl groups containing: up to carbon atoms; aryl, e: g.

phenyl; aralk'yl, e. g. benzyl; alkyloxy, e.lg. methoxy and ethoxy; .aryloxy, e. g. phenoxy; aminosubstitutedby alkyl, aralkyl or aryl groupsne. g. those referred-to above; amino substituted by acyl, e. g. acetamino and sulphonyl amino,

such as p-toluene sulphonyl amino; carboxyl; carboxylic United States Patent 0 2,868,829 Patented Jan. 13, 1959 2, ester, e. g. ethoxy carbonyl; amino-substituted carboxylic ester, e. g. dialkylamin'o alkoxy carbonyl; amino sulhonyl; nitro'; thioatkyl; and oxyalkyl and oxyalkoxy, including polyoxyalkoxy groups.

When the molecular size of the compound is large enough,.e. g. when it contains long chain alkyl groups in the R grouping, such asgroupsv of 10-48 carbon atoms, or when it contains large substituent groups such as diphenoxyphenyl groups, the colour-couplers obtained present the fur therv advantage'that when'introduced into a gelatino silver halide photographic emulsion they have a reduced tendency to migrate from the layer inwhich they are incorporated, either duriri'glke'e'pirig or proeess ng in the case of thes'e long chain' alkyl types dfeemp und it is preferred that the compounds should contain on or two water-solubilising'gr'oups such as carboxylic or sulphonic acid groups, and these may bepresent as further suhstitue'nts in the group R j According to a further aspect of this invention there is aprovidema process of? colour ph'otography" which com- -prises developing a: silver image in'a silver halide' photographic emulsion by means of an aromatic primary amino developing agent in the presence of a colour-coupler as just defined, the said colour-coupler being initially inetude-dun thepnstugraphic 1e ulsion', or'be'ingincluded in the developer-composition. According to a stillfurther aspectof this invention c'olour transparencies producedby the aforesaid process are printed on to multilayer subtractive colour print/material to produce positive prints: thereof in colour. In particular, such colour. transparencies are printedon to multilayer" subtractive colour priiit" material 'of a type image" by the silyer-dye-bleachprocess photography. Y

known per se and adapted to be processed to a positive of colour The following; examples-will serve to-illu'strate the pro duction of colour couplers according to the invention:

EXAMPLE 1 p Preparation of 2:S dimethoxybenzoylacetanilide 2.6 -g. .2:i-dimethoxybenzoylacetic ethyl ester was dissolved in 20; ccsz dry xylene in aflask arranged for'distillation and the solutionheated toboiling. To the boiling solution was slowly added'a solution of 0.93 g. aniline in J 10:-c,es:.xylene containingafewdtOps-of pyridine; the-rate of addition was adjusted to be equal toth'e rate of removal I by distillation of xylene together with the alcohol liberated in the reaction. After complete addition,- the slow distillation was'c'ontinue'd until a further 5 cos. had" been collected. The contents of the flask-were fransferredwhile hot to a beaker and then cooled. When crystallisation ether (B'. P'. 60 and thoroughly cooled. The solid product was-filtered off and purified by recrystallisation from a mixture of benzene and petroleum ether. Colourless crystals, M. P. 13 0" C.

EXAMPL Preparation 0f dir rze'thoxylzenaoylacet-o-clilororzriilide This preparation was conducted; as in Example 1% but using, 113 g. o-chloroaniline in place of- 0.93 g. aniline. The'p'roduct separated as colourless crystalsfrorn a mixture of benzene and petroleum ether. M. P. 156.

EXAMPLE 3 Preparation of 2zj-dimethoxybenzoylacet=0 anisidide This compound was" preparedby the same procedure as in Example 1, usingf1.4 g. o=anisidine in place of 0.93

g. aniline. It separated from benzene-petroleum ether as colourless crystals, M. P. 122-124."

The following examples, 4-15 inclusive, are made by the general procedure of Example 1, substituting for 0.93 g. of aniline the quoted weight of the specified amine.

EXAMPLE 4 Preparation of 2:S-dimethoxybenzoylacet-p-ethoxycarbonyl anilide From 1.65 g. ethyl-p-aminobenzoate. The product was crystallised from a mixture of benzene and petroleum ether to give colourless crystals, M. P. 132 C.

EXAMPLE 5 Preparation of 2:S-dimethoxybenzoylacet-p-carboxyanilide From 1.37 g. p-aminobenzoic acid. The product was recrystallised from aqueous alcohol to give colourless crystals, M. P. 211 C.

EXAMPLE 6 Preparation of 2:S-dimethoxybenzoylacet-o-carboxyanilide From 1.37 g. anthranilic acid. The product was recrystallised from aqueous alcohol to give colourless crystals, M. P. 175 C.

EXAMPLE 7 Preparation of 2:S-a'imethoxybenzoylacet-m carboxyanilide From 1.37 g. m-aminobenzoic acid. The product crystallised from aqueous alcohol as colourless crystals, M. P. 180 C.

EXAMPLE 8 Preparation of 2:S-dimethoxybenzoylacet-p-(diethylaminoethoxycarbonyl) anilide From 2.36 g. fl-diethylaminoethyl p-aminobenzoate.

4 tallised from alcohol to give pale yellow crystals, M. P. 166 C.

EXAMPLE 15 Preparation of 2:S-dimethoxybenzoylacet-p-acetamino anilide From 1.5 g. p-aminoacetanilide. The product separated from alcohol as colourless crystals, M. P. 218 C.

EXAMPLE 16 EXAMPLE 18 Preparation of 2:5 -diethoxybenzoylacet-o-toluidide The compound was prepared, by reacting in xylene by the procedure of Example 1, 2.9 g. ethyl 2:5-diethoxy- The compound separated as colourless crystals from a mixture of benzene and petroleum ether, M. P. 94 C.

EXAMPLE 9 Preparation of 2:S-dimethoxybenzoylacet-p-sulphanamido anilide From 1.72 g. sulphonilamide. Separated as buff needles from aqueous alcohol, M. P. 200 C.

EXAMPLE 10 Preparation of 3-(2':5-dimeth0xy benzoylacetamido)-4- methyloctadecylaminobenzoic acid From 4.18 g. 3-amino-4-methyloctadecylaminobenzoic acid. Crystallised from benzene as colourless crystals, M. P. 130 C.

EXAMPLE 11 Preparation of N-(2:5-dimethoxybenzoylacetyl)-N'-(ptoluenesulphonyl)-p-phenylenediamine The product was recrystallised from alcohol to give colourless crystals, M. P. 183 C.

EXAMPLE 12 Preparation of 2':5'-dimethoxybenzoylacet-Z:4-di-o-cresoxyanilide From 3.1 g. 2:4-di-o-cresoxyaniline. The product was recrystallised from benzene to give colourless crystals, M. P. 108 C.

EXAMPLE 13 Preparation of 2:S-dimethoxybenzoylacet-p-thioanisidide From 1.4 g. p-aminothioanisole. The product separated from benzene as colourless crystals, M. P. 136 C.

EXAMPLE 14 Preparation of 2:S-dimethoxybenzoylacet-p-nitranilia e From 1.38 g. p-nitraniline. The product was recrysbenzoylacetate and 1.1 g. o-toluidine. Recrystallised from carbon tetrachloride as colourless crystals, M. P. 137 C.

EXAMPLE 19 Preparation of 2:5-a'iethoxybenzoylacet-o-anisidide The preparation Was efiected as in Example 3 but using 2.9 g. ethyl-2:S-diethoxybenzoylacetate in place of 2.6 g. ethyl-2:S-dimethoxybenzoylacetate. The product was recrystallised from aqueous alcohol. M. P. C.

EXAMPLE 20 Preparation of 2:5-diethoxybenzoylacet-2':4'-xylidide The compound was prepared by reacting together in xylene by the general procedure of Example 1, 2.9 g. ethyl 2:S-diethoxybenzoylacetate and 1.25 g. m-4-xylidine. It was recrystallised from alcohol as colourless crystals, M. P. 134 C.

EXAMPLE 21 Preparation of 2:S-diethoxybenzoylacet-p-anisidide The preparation was conducted as in Example 19 but using p-anisidine instead of o-anisidine. The product separated from alcohol as colourless crystals, M. P. 168 C.

EXAMPLE 22 Preparation of 3(2':5'-diezhoxybenzoylacetamido)-4- methyloctadecylaminobenzoic acid Prepared as in Example 10 but using 2.9 g. ethyl 2:5- diethoxybenzoylacetate in place of 2.6 g. ethyl 2:5-dimethoxybenzoylacetate. Recrystallised from benzene as colourless crystals. M. P. C.

EXAMPLE 23 Preparation of 2:5-diethoxybenzoylacet-p-carboxyanilide Prepared as in Example 5 but using 2.9 g. ethyl 2:5- diethoxybenzoylacetate in place of 2.6 g. ethyl 2:5-di- 'methoxy benzoylaceta'te. The product crystallised from aqueous alcohol as colourless crystals. M. P. 187 C.

The following example will serve to illustrate the use of the colour couplers of the invention in the production .pf colour developed yellow dye images:

EXAMPLE 24 I A photographic carrying a gelatino silver bromide Sodium carbonate d'ecahydratenu,.. ..g 40 Sodium hexametaphosphate g- 1.5 Sodium. sulphite v g Industrial'ethyl alcohol' cc 50 Potassium bromide 1 Colour coupler Water to make 500 cc.

The developed film was then rinsed and bleached in Farmers reducer to remove residual silver and silver bromide, washed and dried, aifording a yellow image negative with respect to the original subject to which the film was exposed.

As stated above, the dyestuifs obtained from the colourcouplers of this invention have a reduced transparency to violet and ultra-violet radiation.

When yellow dye images'are produced using the colour couplers of this invention and are then printed on to multilayer colour print material of the type adapted to be processed by the silver-dye-bleach process of colour photography, the density of the yellow print image (over the range up to but not including the maximum density) is substantially greater for a given density level of yellow dye derived from a colour coupler of the present invention than from the same density level of yellow dye derived from a colour coupler of the prior art.

The property of reduced transparency to violet and ultra-violet radiation and the results obtained when the dyes are printed as just described are set out in the following Tables I and II.

The compound first named in Table. I is a typical colour coupler 'oftliei nonesubsftantivetype knownj per se, while the compound first named in Talllelf lsa' typical substantive colour couplerknown' per se'; and theseare included as comparison compounds? The foregoingflensities were determinedtqlight passing an Ilfbrd Cbl our Filter No. 304i '(Tlieword Ilford is a registered trademarl) Smoothe -dyes derived from colour? couplers according to this-invention; are? more 10 absorbtive of ultra-violet radiation, less of such radiation is transmitted from the printing light source through the dye image to the print material. The extent of exposure of the ultra-violet-sensitive layer of the print material is thus reduced so that there is less bleaching of dyestutf by the silver developed therein and accordingly a higher density of dyestufi is obtained.

What we claim is: 1. A colour-coupler of the general'formula:

TABLE I Relgtlggedgliities Density Density Colour-former 93113113- Dlgle'ilgz D.2/D.1

440 mp 385 m Dye D 1 2:4-Dichloroacetoacetanilide 1.0 0. 3 3i 8: 2z5-Dimethoxybenzoylacet-o-chloroanilide 1.0 0.77 82%; 3: 8:3; 2:5-Dimethoxybenzoylacet-anjlide 1.0 0.87 8:12 8: {a 2:fi-Dimethoxybenzoylacet-o-anisidide 1.0 0.88 8: 8: 2:5-Diethoxybenzoylacet-anilide 1.0 0.88 2:5-Diethoxybenzoylaeet-0-toluidide 1.0 0.87 83 2:5-Diethoxybenzoylacet-o-chloroanilide 1.0 0.79 9:?8 32 2:5-Diethoxybenzoylacet-o-anlsldide 1.0 0.89 8: 8:35 1g; 2:5-Diethoxybenzoylacet-2:4-xylidide 1. o o. 3; 8g 8: 3g 2:5-Dlethoxybenzoylacet-p-anisidlde 1. 0 1. 00 2:5-Dimethoxybenzoylacet-p-ethoxycarbonylanillde 1.0 0.83 812g 8: g: 2:5-Dimethoxybenzoylacet-p-earboxyanilide 1.0 0.89 8: g: 8 3; 2:5-Diethoxybenzoylacet-p-carboxyanillde 1.0 0.91 2:5-Dimethoxybenzoylacet-o-carboxyanllide 1.0 0.93 8: 83% i: 2:fi-Dimethoxybenzoylacet-m-carboxyanilide 1.0 0.80 8:82 0.43 0. 40 222:eazaetrrszestrril iarrsrswenzbonyl)an1l1de 1.0 1.25 0.78 0.70

TABLE II Relgtlggedseii ities Density Density Colour-former (floorllzg- Dggilit 2 D.2/D.1

440 I111: 385 mp Dye D 1 @0 fiiit????? ff ffffffi ffffiffflitfi 1... 0.... 9-1; g g-gg 3 (2'25 Diethoxyb do) -4-methyloctadecylamlnobenzoic acid 1.0 1.36 8 :83 8(2:5-D1methoxy benzoylacetamldo)-4-methyloet ylaminobenzoie acid 1.0 1.35 2':5-Dimethoxybenzoylacet-2z-di-o-cresoxyanflide 1.0 1.40 g: 3: 32

, 7 4. 3 (2'z5' dimethoxybenzoylacetamido) 4 methyloctadeyl-aminobenzoic acid. 5. 2:5 diethoxybenzoylacet o chloroanilide. 6. 2:5 diethoxybenzoylacet p carboxyanflide,

' 'Refrences Cited inthe file of this patent UNITED STATES PATENTS 2,347,722 Wenner May 2, 1944 Sparks Oct. 24, 1944 Bavely July 2, 1946 Weissberger et a1. Sept. 3, 1946 Bavely Dec. 3, 1946 McCrossen et a1 Sept. 15, 1953 McCrossen et a1. Dec. 27, 1955 

1. A COLOUR-COUPLER OF THE GENERAL FORMULA: 